Polymerizable compositions and articles produced therefrom and method

ABSTRACT

A polymerizable composition of polyester resin plus monomer having an ethylenic double bond and a catalyst in the form of a tertiary butyl perester of a chlorinated aliphatic monoacid having from 3 to 12 carbon atoms, and shaped articles and method for producing same.

United States Patent [1 1 Chretien et a1.

[ Jan. 14', 1975 POLYMERIZABLE COMPOSITIONS AND ARTICLES PRODUCED THEREFROM AND METHOD Inventors: Gilbert Chretien, Chauny; Philippe Girard, Autrevillej, Jean-Marc Lamy, Villequier-Aumont; Christophe Menard, Sinceny, all of France I Assignee: Rhone-Progil, Paris, France Filed: Oct. 5, 1972 Appl. No.: 295,266

Foreign Application Priority Data Oct. 6, 1971 vs. Cl 260/40 R, 260/453, 260/861 Int. Cl C08g 17/16 Field of Search... 260/861, 863, 453 R,

France 71.35950 [5 6] References Cited UNITED STATES PATENTS 2,661,363 12/1953 Dickey 260/453 R 3,079,363 2/1963 Koch et al. 260/863 X 3,408,423 10/1968 Friedman et al 260/861 X 3,644,612

2/1972 Meyer et a1 260/863 X Primary ExaminerMorris Liebman Assistant ExaminerS. M. Person 14 Claims,'No Drawings POLYMERIZABLE COMPOSITIONS AND ARTICLES PRODUCED THEREFROM AND METHOD The present invention relates to new compositions of polyester resins and monomers which are copolymerizable at medium and high temperatures and it relates particularly to a catalytic system for these compositions.

Unsaturated polyesters are generally copolymerized with vinylic monomers in the presence of catalysts such as benzoyl peroxide or ketone peroxides. These catalysts cannot be introduced into the composition a long time before polymerization and/or require the addition, before this operation, of a compound which modifies the action of the catalyst.

Applicants have obtained and it is an object of this invention to provide new compositions containing a class of catalysts which have not hitherto been used for fixing vinylic or allylic monomers onto an unsaturated alkyd chain, and which case the conditions for application of these resins. They can also be incorporated in the composition long before use of the resin, which consequently can be stored without change at close to ambient temperature, even in the presence of conventional accelerators such as cobalt naphthenate.

In accordance with one aspect of the invention, there is provided a polymerizable composition, which comprises an unsaturated polyester, at least one monomer having an ethylenic double bond, and a catalyst comprising a tertiary butyl perester of a chlorinated aliphatic monoacid, having from 3 to 12 carbon atoms.

Examples of such peresters are tertiobutyl perchloropropionate, tertiobutyl perdichloropropionate, tertiobutyl perchlorodecanoate and tertiobutyl pertrichloroacrylate.

The peresters are generally dissolved during their preparation in an organic solvent, preferably a phthalate, and especially dimethyl phthalate. The content of catalyst, expressed as the weight of active oxygen in the solution, is preferably from 2% to 6%. The amount of catalyst present in the composition, expressed as active oxygen, is preferably from 0.05% to 0.2% by weight of the constituents.

In addition to the polyester, usually obtained by condensation of at least one polycarboxylic acid and at least one polyol or an internal ether oxide, and containing ethylenic double bonds and at least one vinylic or allylic monomer and a catalyst, the composition may contain accelerators and different ingredients, such as a colorant or a filler generally used in such resins. The compounds, of which part must be unsaturated, giving unsaturated polyester chains by polycondensation, as well as the vinylic or allylic monomers ensuring reticulation of these chains, can be chosen, for example, among those mentioned in pages 13 to 40 ofPolyester Resins (Lawrence), published in 1960 by Reinhold Publishing Corporation, New York. The other possible ingredients of the resins, apart from the catalysts, are also mentioned in this work. The accelerators, preferably used, are organic salts of vanadium and cobalt, particularly naphthenates. The content by weight of these compounds, when present, is from 0.05% to 0.2% of the total composition. Alkoylaromatic amines are also active accelerators for the majority of these catalysts at medium temperature (5080C).

The compositions obtained, particularly containing cobalt naphthenate, can be stored for more than 24 hours at 25C, whereas with a ketone peroxide, the period of storage cannot exceed 2 hours.

Such compositions can be used notably for stratified articles at medium temperature (5080C) or for articles formed by pressing (80-l20C). At medium temperatures an accelerator is incorporated in the composition; the catalyst should not be accelerated at high temperatures.

In order to further explain the action of these catalysts, two tables are given below quantitively showing the results of this action.

The catalyst is introduced in a resin comprising polypropylene glycol maleophthalate and 37% of styrene on the total weight of the resin; the viscosity, at 25C, is 4 poises. The catalysts are used in an amount to give 0.076% of active oxygen in the total weight of resin. Table I gives the gelling time at 50C.

Table II gives the gelling time at C.

TABLE ll Gelling time without Catalyst accelerator Tertiobutyl permonochloropropionate 25 minutes Tertiobutyl perchloropropionate 2] minutes Tertiobutyl perchlorodecanoate 14 minutes Tertiobutyl pettrichloroacrylate 25 minutes The following examples are given by way of illustration, but not by way of limitation:

EXAMPLE 1 This example describes the use of the composition of the invention in the manufacture of sheets of polyester reinforced with glass fibers.

This manufacturing process consists of impregnating a mat of glass fibers with a catalyzed resin and polymerizing this resin in a tunnel oven in a continuous process.

In order to carry out the impregnation, a transparent cellulose film, known under the commercial name of Cellophane, 4O cm/wide, is transported by means of a train of rollers in conventional manner on a flat, horizontal table at a speed of 40 cm/minute. l 10 grams per minute of resin, spread by means of a horizontal knife, is fed to the film and a glass fiber mat of the same width, weighing 450 g/m is applied to the film. A second cellulose film identical to the first is then stretched over the mat. The gap of 1 mm, between the roller applying the second film and the table, determines the thickness of the sheet. A distance of 60 cm is provided between the zone of the table at which the mat is applied and the entrance to the oven. The temperature in this zone is held at 30C which allows a uniform impregnation of the mat. The heated tunnel is arranged along an extension of the table and comprises four We claim:

1. A polymerizable composition, which comprises an unsaturated polyester, at least one monomer having an ethylenic double bond, and a catalyst comprising a ter- Ovens f 60 Cm length arrangfid Side by f 5 tiary butyl perester of a chlorinated aliphatic mono- The resin Use iS miXtlll'e having a vlscoslty of 4 acid, the acid having from 3 to 12 carbon atoms, the poises at of P y-P py glycol maleophthalate catalyst being present in an amount within the range of and 37% 0f the Weight of the resin of styrene, to which 0.05 to 0.2% based on the weight of the active oxygen a chlorinated tertiobutyl perester in solution in methyl to the total weight f the polyester and monomer- Phthalate is added in an amount Provide a content 2. A composition as claimed in claim 1 in which the of active oxygen of 015%, and Optionally accelera' catalyst is selected from the group consisting of t-butyl tor of from 9 to 03% of CPbalt or Vanadmm l P peroxychloropropiohate, t-butyl peroxydichloroprothenate. Th1s resm also contains 0.2 parts per m1ll1on pionate, t butyl peroxychlorodecanoate and hbuwl of copper and 70 parts per m1ll1on by weight of hydroperoxytrichloroacrylate qum one. V g 3. A composition as claimed in claim 1 in which the The operating conditions and the results are given in polyester is poly-propylene glycol maleophthalate. the following Table III. 4. A composition as claimed in claim 1 in which the TABLE III Parts per Oven temperature Distance from Distance Temper- Hardness million by in vacuum in C the gellififrom the ature Barcol weight of cation zone at exothermic of peak Peroxides cobalt and/or Two first Others the oven peak to in "C vanadium in the ovens entrance in cm the oven composition FIIU'BHCB lll cm t-butyl peroxydecanoate 50 (Co) 80 8O 75 130 M4 55 (Co) 90 100 80 143 160 45 0 90 100 150 212 151 48 t-butyl 50 (v) 80 so 60 200 92 50 Peroxychloropropionate 0 100 100 126 240 126 30 t butyl peroxytrichloroacrylate 30 (Co) 100 100 90 lso '69 50 The Barcol hardness is measured according to the monomer is styrene. h d ib d b h AFNOR (NF P 38-501) 5. A composition as claimed in claim 1 in which the standard 15 minutes after leaving the oven. The sheets catalyst is added to the composition as a solution in a are smooth and are free from structural faults. liquid phthalate.

6. A composition as claimed in claim 1 in which the EXAMPLE 2 composition contains at least one accelerator.

This example describes the use of the composition of 7. A composition as claimed in claim 6 in which the the invention in the manufacture of serving trays reinaccelerator is an organic salt of vanadium or cobalt. forced by glass fibers. 8. A composition as claimed in claim 7 in which the ln half ofa mold of chrome steel for making sheet 43 accelerator is present in an amount within the range of cm long and 30 cm wide, having an inclined border of 0.05% to 0.2% by weight of the composition.

1 cm and a thickness of 0.3. Cm, there are placed two 9. A composition as claimed in claim 6 in which the supfirposed glass mats having a weight of 450 g/ Cut accelerator is an alkoylaromatic amine.

to the dimensions of the mold. There is then added 186 10, A h d f ki h d i l hi 8 Ofa composition Ofa resin Containing 72% y Weight prises forming a composition as claimed in claim 1 to of P y-P py glycol maleophthalate and 28% 0f the desired shape and heating the composition at a temstyrene (the mixture has a viscosity of 30 poises at peramre i hi h range f 80 120C 25C) to which has been added a quantity of tertiobutyl 11 A method f making Shaped i l hi h perchlorqdecanoate Such that F Commit by gh 9 prises forming a composition claimed in claim 6 to deactive oxygen in the Composition is sired shape and heating the composition at a tempera- A die of corresponding shape is applied by means of ture i hi h range of 50 3()C a press at a Pressure of 43 kg/cmi The mold is held at 12. A method as claimed in claim 10 which includes 100C for 2 flu the step of impregnating a mass of glass fibers with the The trays obtained have, after 15 minutes cooling, a Composition d i h i Barcol hardness of 40. 13. Shaped articles produced by the method claimed It will be understood that changes may be made in i l i 10, the details of formulation and operation without de- 14. Shaped articles produced by the method claimed parting from the spirit of the invention, especially as i l i 12, defined in the following claims.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,860, 555 Dated January 14, 1975 Inventor(s) Gllbert aillen et a1.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

column 2, Table I, under "Catalyst" cancel "t-butyl peroxy dichloropropionate" and substitute t-butyl peroxy chloropropionate--;

cancel "tbutyl peroxy propionate" and substitute t-butyl dichloropropionate cancel "t-butyl peroxydichloropropionate" and substitute t-butyl peroxychloroacrylate column 2, Table I, under"Ge lling time without accelerator" in line 28, before '1 hour" insert column 2, Table II, under "catalyst" cancel "tertiobutyl perinonochloro'propionate" and substitute t-butyl peroxychloropropionate canbel "tertiobutyl perchloropropionate and substitute t-butyl dichloropropionate cancel "tertiobutyl perchlorodecanoate" and substitute t-butyl peroxychlorodecanoate cancel "tertiobutyl pertrichloroacrylate" and substitute t-butyl peroxychloroacrylate Signed and Sealed this third Day of February1976 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN .Atresting Officer Commissioner oj'latents and Trademarks 

2. A composition as claimed in claim 1 in which the catalyst is selected from the group consisting of t-butyl peroxychloropropionate, t-butyl peroxydichloropropionate, t-butyl peroxychlorodecanoate and t-butyl peroxytrichloroacrylate.
 3. A composition as claimed in claim 1 in which the polyester is poly-propylene glycol maleophthalate.
 4. A composition as claimed in claim 1 in which the monomer is styrene.
 5. A composition as claimed in claim 1 in which the catalyst is added to the composition as a solution in a liquid phthalate.
 6. A composition as claimed in claim 1 in which the composition contains at least one accelerator.
 7. A composition as claimed in claim 6 in which the accelerator is an organic salt of vanadium or cobalt.
 8. A composition as claimed in claim 7 in which the accelerator is present in an amount within the range of 0.05% to 0.2% by weight of the composition.
 9. A composition as claimeD in claim 6 in which the accelerator is an alkoylaromatic amine.
 10. A method of making shaped articles which comprises forming a composition as claimed in claim 1 to the desired shape and heating the composition at a temperature within the range of 80*-120*C.
 11. A method of making shaped articles which comprises forming a composition claimed in claim 6 to desired shape and heating the composition at a temperature within the range of 50*-80*C.
 12. A method as claimed in claim 10 which includes the step of impregnating a mass of glass fibers with the composition during shaping.
 13. Shaped articles produced by the method claimed in claim
 10. 14. Shaped articles produced by the method claimed in claim
 12. 